CN108598443A - Pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material and preparation method thereof - Google Patents
Pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material and preparation method thereof Download PDFInfo
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- CN108598443A CN108598443A CN201810557051.2A CN201810557051A CN108598443A CN 108598443 A CN108598443 A CN 108598443A CN 201810557051 A CN201810557051 A CN 201810557051A CN 108598443 A CN108598443 A CN 108598443A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material and preparation method thereof, the negative material is made of following methods：（1）Source of iron, zinc source, sulphur source and ternary organic carboxyl acid are added to the water, stirring and dissolving to uniform solution；（2）Sealing, carries out heating reaction, cooling, filters, and washs, dry, obtains black powder；（3）In an inert atmosphere, it roasts, it is cooling, obtain pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material.Zinc sulphide and ferrous sulfide in pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material of the present invention are pure phase, and second particle grain size is 5~8 μm, and the duct containing 0.1~2.0 μm of diameter；Battery is assembled them into, the stable structure in charge and discharge process, volume expansion is small, good conductivity, discharge and recharge reaction high reversible, and has excellent high rate performance；The method of the present invention is easy, and raw material cost is low, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of cathode material of lithium ion battery and preparation method thereof, and in particular to a kind of pore sphere sulphur
Change zinc/ferrous sulfide/carbon negative pole material and preparation method thereof.
Background technology
Development with people to the increase and commercial li-ion battery of portable equipment demand, the at present graphite cathode of mainstream
It can no longer meet demand of the people to capacity of lithium ion battery.Iron and zinc are all cheap metals, and sulfide is as lithium ion
When cell negative electrode material, there is higher theoretical specific capacity, still, structure is easily caved in charge and discharge process, influences specific volume
Amount and cycle performance.
CN104882604B discloses a kind of ZnS-Al2O3/ N-C combination electrode materials and preparation method, the combination electrode material
Material is by zinc sulphide ZnS nanocrystalline, unformed aluminium oxide Al2O3It is formed with nitrogen-doped carbon N-C three parts, wherein ZnS is electrochemistry
Active material, grain size are 2~3nm, and N-C can improve the electric conductivity of composite material, and unformed Al2O3Barrier ZnS is then played to fill
The effect reunited in discharge process, it is forthright that the synergistic effects of three kinds of components makes combination electrode material show height ratio capacity, high power
It can be with high circulation stability.But under 0.2A/g current densities, ZnS-Al2O3/ N-C first circle charging quality specific capacities are
663.7mAh/g, first circle efficiency are only 58%, i.e., first effect is relatively low, and commercialized possibility is relatively low.
CN105355890 A disclose a kind of preparation method of negative electrode of lithium ion battery zinc sulphide-graphene composite material
And application, it is that ZnS-RGO composite materials are obtained as new type lithium ion battery cathode by fabricated in situ, centrifugation, drying.Though
It is so tested under the current density of 40mA/g, first circle specific discharge capacity is 1126.6mAh/g, and still, which is recycling
After 100 circles, discharge capacity is only 250mAh/g, and stable circulation performance is poor.
CN103274474A discloses a kind of rod-shaped zinc ferrite and preparation method thereof, the rod-shaped zinc ferrite it is a diameter of
7.0~500nm, draw ratio are 3.0~20, and rod-shaped radial direction is made of 1~20 nano particle, and the size of single nanoparticle is
7.0~30nm；It is raw material that the preparation method, which selects ferrous sulfate and zinc chloride, using oxalic acid as precipitating reagent, carries out precipitation at room temperature,
After hybrid reaction, aged, centrifugation, washing, dry and heat treatment obtain the rod-shaped zinc ferrite constructed by nano particle.Although
The material has excellent chemical property, and still, during preparation, solution is added dropwise and ageing is required to isolation air,
It is higher to environmental requirement, it is unfavorable for mass production.
CN103413941A discloses a kind of lithium ion battery negative material and preparation method thereof, and the lithium ion battery is negative
Pole material uses hydrothermal reaction at low temperature, and using lauryl sodium sulfate as surfactant, soluble ferrite and urea are raw material,
Micro/nano level ferrous carbonate negative material is prepared under certain temperature and time.Although the material preparation method is simple,
It is, by gained ferrous carbonate negative material first Application in lithium ion battery, at 0.05~3.0V, 200mA/g current densities
First discharge specific capacity reaches 900~1110mAh/g, by 100 cycle specific discharge capacity only 585~640mAh/g, material
Cycle performance it is poor.
Invention content
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide one kind in charge and discharge
Stable cycle performance in electric process, capacity is higher, and preparation method is simple, and raw material cost is low, is suitable for industrialized production
Pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is as follows：Pore sphere zinc sulphide/ferrous sulfide/carbon is negative
Pole material, is made of following methods：
（1）Source of iron, zinc source, sulphur source and ternary organic carboxyl acid are added to the water, stirring and dissolving to uniform solution；
（2）By step（1）Acquired solution seals, and carries out heating reaction, cooling, filters, and washs, dry, obtains black powder；
（3）By step（2）Gained black powder in an inert atmosphere, roasts, cooling, obtain pore sphere zinc sulphide/ferrous sulfide/
Carbon negative pole material.
Preferably, step（1）In, the molar ratio of ferro element and Zn-ef ficiency in zinc source is 1 in the source of iron:1~3（It is more excellent
Select 1:1.5~2.5）.If the ratio is excessive, which easily reunites, and forms larger particle, if the ratio is too small,
It is unfavorable for the reasonable utilization of resource.
Preferably, step（1）In, the molar ratio of the sum of the sulphur source and ferro element and Zn-ef ficiency molal quantity is 1~5:1.
If the ratio is too small, be difficult to metal complete cure, the upper limit of the ratio be avoid generating excessive free state sulphur it is attached
It in material surface, influences material property.
Preferably, step（1）In, the molar concentration of the sum of the ferro element and Zn-ef ficiency molal quantity in uniform solution is
0.08~1.0 mol/L（More preferable 0.1~0.5 mol/L）.If the concentration is too low, it is difficult to generate progress next step experiment
Material can directly generate precipitation if the excessive concentration, uniform solution can not be formed.
Preferably, step（1）In, molar concentration of the ternary organic carboxyl acid in uniform solution is 0.08~1.0
mol/L（More preferable 0.1~0.5 mol/L）.If the concentration is excessive, reaction product phosphorus content is higher, influences material capacity,
If the concentration is too small, it is difficult to metallic zinc, iron and sulphur source being complexed, generates many free metal ions.
Preferably, step（1）In, the source of iron is organic source of iron.
Preferably, organic source of iron is one or more of ferric acetyl acetonade, ironic citrate or ferrocene etc..It is organic
On the one hand source of iron is capable of providing source of iron, on the other hand, if using inorganic source of iron, be difficult to generate porose structure.
Preferably, step（1）In, the zinc source is inorganic zinc source.
Preferably, the inorganic zinc source is one kind in zinc sulfate, zinc nitrate or zinc chloride and their hydrate etc.
Or it is several.
Preferably, step（1）In, the sulphur source is organic sulphur source.
Preferably, organic sulphur source is one or more of thioacetamide, thiocarbamide or L-cysteine etc..
Preferably, step（1）In, the ternary organic carboxyl acid is citric acid and/or Trimesic acid etc..Iron ion, zinc
With ternary organic carboxyl acid complexation reaction can occur for ion, can form matching for metal ion-ternary organic carboxyl acid-metal ion combination
Object is closed, so that during sintering, the carbon that ternary organic carboxyl acid is formed can be compound uniformly with sulfide.
Preferably, step（2）In, the temperature of the heating reaction is 120~250 DEG C（More preferable 160~200 DEG C）, when
Between be 6~24 h（More preferable 10~20 h）.The lower limit of the temperature is that the hydrogen being more advantageous in water generates hydrogen sulfide with sulphur source,
The upper limit of the temperature is to be more advantageous to the safety of hydro-thermal reaction；The lower limit of the time is to be more advantageous to using thio second
When amide is sulphur source, product can all be vulcanized, and the upper limit of the time is to be more advantageous to when using thiocarbamide, and product is complete
Vulcanization, and do not waste time.
Preferably, step（2）In, the mode of the washing is to be taken up in order of priority cross washing filtrate >=2 with ethyl alcohol and water
It is secondary.
Preferably, step（2）In, the temperature of the drying is 60~100 DEG C, and the time is 10~40 h（More preferable 12~
30 h）.
Preferably, step（3）In, the temperature of the roasting is 400~600 DEG C, and the time is 2~6h.In roasting process,
Material surface is left in the sulphur distillation of free state, realizes the removal of free state element sulphur, and convert organic matter therein to carbon source.
Preferably, step（3）In, the inert atmosphere is argon gas or nitrogen atmosphere etc..The argon gas or nitrogen are pure
The high-purity argon gas or high pure nitrogen of degree >=99.99%.
It is of the present invention to be cooled to cooled to room temperature.
Preferably, the second particle grain size of the pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material is 5~8 μm,
And the duct containing 0.1~2.0 μm of diameter.
The present invention technical principle be：Tapped a blast furnace zinc complex sulfide by high-temperature solution method preparation, wherein source of iron with zinc
Can be relatively also easy to produce during source is compound with cavity sphere material, although so that the material on micro-meter scale,
But it can still realize the good infiltration with electrolyte, larger space is provided for the shuttle of lithium ion, and its micrometer structure can
The material is kept still to keep stable chemical property under longer cycle；And using ternary organic carboxyl acid as carbon source and network
Mixture can generate the uniform compound zinc sulphide/ferrous sulfide/carbon negative pole material of carbon, be easy to generate stable SEI after sintering
Film, to effectively prevent solvent molecule by while, make Li+Freely it can be embedded in and deviate from.
Beneficial effects of the present invention are as follows：
（1）Pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material of the present invention is formed with carbon by zinc sulphide and ferrous sulfide
The composite material mutually mixed, zinc sulphide and ferrous sulfide therein are pure phase, without other impurity, secondary of the composite material
Grain grain size is 5~8 μm, and the duct containing 0.1~2.0 μm of diameter, and larger duct is more advantageous to electrolyte and negative material
Effective contact, shorten transmission path of the lithium ion in negative material, and larger grain size can be kept in charge and discharge process
Rock-steady structure is conducive to lithium ion and shuttles in stablizing for charge and discharge process, along with uniform multiple between metal sulfide and carbon
It closes so that electrode reaction can be maintained at the state of a high reversible；
（2）Pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material of the present invention is assembled into battery, charging/discharging voltage be 3~
0.01V, current density are under 50mA/g, and the first discharge specific capacity of institute's assembled battery may be up to 969.3mAh/g, and head effects can be high
Up to 84.5%；Under 1A/g current densities, after being recycled to 1000 circles, specific discharge capacity highest may remain in 722.3mAh/g, library
Human relations efficiency is up to 99.0%, and under the high current density of 10A/g, highest still maintains the specific discharge capacity of 136.1mAh/g, says
Bright material is capable of the stabilization of holding structure in charge and discharge process, and volume expansion is small, good conductivity, makes discharge and recharge reaction height can
It is inverse, and there is excellent high rate performance, it can adapt to the process of high current charge-discharge；
（3）The method of the present invention is easy, does not use high low cost materials as graphene, raw material cost is low, is suitable for industry
Metaplasia is produced.
Description of the drawings
Fig. 1 is the XRD diagram of 1 gained pore sphere zinc sulphide of the embodiment of the present invention/ferrous sulfide/carbon negative pole material；
Fig. 2 is the SEM figures of 1 gained pore sphere zinc sulphide of the embodiment of the present invention/ferrous sulfide/carbon negative pole material；
Fig. 3 be 1 gained pore sphere zinc sulphide of the embodiment of the present invention/ferrous sulfide/carbon negative pole material discharge cycles curve and
Coulombic efficiency figure；
Fig. 4 is the SEM figures of 2 gained pore sphere zinc sulphide of the embodiment of the present invention/ferrous sulfide/carbon negative pole material；
Fig. 5 is the high rate performance figure of 2 gained zinc sulphide of the embodiment of the present invention/ferrous sulfide/carbon negative pole material；
Fig. 6 is the first charge-discharge curve graph of 3 gained zinc sulphide of the embodiment of the present invention/ferrous sulfide/carbon negative pole material.
Specific implementation mode
With reference to embodiment and attached drawing, the invention will be further described.
The purity of high-purity argon gas or high pure nitrogen used in the present embodiment is 99.99%；The embodiment of the present invention is used
Raw material or chemical reagent obtained unless otherwise specified by routine business approach.
Embodiment 1
（1）By 2 mmol ferric acetyl acetonades, 3 mmol zinc nitrate hexahydrates, 5 mmol thioacetamides and 2.5 g（13mmol）
Citric acid is added in 50 mL deionized waters, stirring and dissolving to uniform solution；
（2）By step（1）Acquired solution is poured into 100 mL polytetrafluoroethylene (PTFE) pyroreaction kettles, and box hat sealing is placed in air blast baking
In case, 180 DEG C are heated to, reacts 16 h, cooled to room temperature, filtering is taken up in order of priority intersection with ethyl alcohol and deionized water and is washed
It washs filtrate 4 times, then is placed in 60 DEG C of convection ovens, dry 24 h obtain black powder；
（3）By step（2）Gained black powder is in high-purity argon gas atmosphere, at 600 DEG C, roasting 3h, and cooled to room temperature,
Obtain pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material.
As shown in Figure 1, the vulcanization in pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material obtained by the embodiment of the present invention
Zinc and ferrous sulfide are pure phase, without other impurity.
As shown in Fig. 2, secondary of pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material obtained by the embodiment of the present invention
Grain size is 6 μm, and the duct containing 1.0 μm of diameter.
The assembling of battery：Weigh pore sphere zinc sulphide/ferrous sulfide/Carbon anode material obtained by the 0.40g embodiment of the present invention
Material, addition 0.05g acetylene blacks make conductive agent and 0.05g N-Methyl pyrrolidones make binder, after mixing, are applied to copper foil
On negative plate is made, in vacuum glove box with metal lithium sheet be anode, using lithium electric separator as diaphragm, 1mol/L LiPF6/EC:
DMC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
From the figure 3, it may be seen that being 3~0.01V in charging/discharging voltage, current density is under 50mA/g（Preceding 3 circle）, institute's assembled battery
First discharge specific capacity be 923.5mAh/g, initial charge specific capacity be 780.4mAh/g, head effect be 84.5%；It is close in electric current
Degree is under 1A/g（Since enclosing the 4th）, after being recycled to 1000 circles, specific discharge capacity remains at 716.1mAh/g, coulombic efficiency
It is 99.0%, illustrates that material is capable of the stabilization of holding structure in charge and discharge process, volume expansion is small, and good conductivity makes charge and discharge
Reaction height is reversible.
Embodiment 2
（1）By 2 mmol ferric acetyl acetonades, 3 mmol zinc nitrate hexahydrates, 5 mmol thioacetamides and 2 g（9.52mmol）
Trimesic acid is added in 50 mL deionized waters, stirring and dissolving to uniform solution；
（2）By step（1）Acquired solution is poured into 100 mL polytetrafluoroethylene (PTFE) pyroreaction kettles, and box hat sealing is placed in air blast baking
In case, 200 DEG C are heated to, reacts 10 h, cooled to room temperature, filtering is taken up in order of priority intersection with ethyl alcohol and deionized water and is washed
It washs filtrate 3 times, then is placed in 100 DEG C of convection ovens, dry 20 h obtain black powder；
（3）By step（2）Gained black powder is in high-purity argon gas atmosphere, at 450 DEG C, roasting 5h, and cooled to room temperature,
Obtain pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material.
After testing, the zinc sulphide in pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material obtained by the embodiment of the present invention and
Ferrous sulfide is pure phase, without other impurity.
As shown in figure 4, secondary of pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material obtained by the embodiment of the present invention
Grain size is 5~8 μm, and the duct containing 0.1~1.0 μm of diameter.
The assembling of battery：Weigh pore sphere zinc sulphide/ferrous sulfide/Carbon anode material obtained by the 0.40g embodiment of the present invention
Material, addition 0.05g acetylene blacks make conductive agent and 0.05g N-Methyl pyrrolidones make binder, after mixing, are applied to copper foil
On negative plate is made, in vacuum glove box with metal lithium sheet be anode, using lithium electric separator as diaphragm, 1mol/L LiPF6/EC:
DMC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
As shown in figure 5, being 3~0.01V in charging/discharging voltage, current density is under 50mA/g, and first discharge specific capacity is
955mAh/g, initial charge specific capacity are 759.2 mAh/g, and head effects are 79.5%, illustrate that material can be protected in charge and discharge process
The stabilization of structure is held, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible；Under the high current density of 10A/g,
The material still maintains the specific discharge capacity of 136.1mAh/g, illustrates that the material has excellent high rate performance, can adapt to big
The process of current charging and discharging.
After testing, it is 3~0.01V in charging/discharging voltage, current density is under 1 A/g, and institute's assembled battery is recycled to 1000
After circle, specific discharge capacity remains at 706.7 mAh/g, and coulombic efficiency is 98.6 %, illustrates material energy in charge and discharge process
The stabilization of enough holding structures, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
Embodiment 3
（1）By 2.5 mmol ironic citrates, 5 mmol, six chloride hydrate zinc, 22.5 mmol thiocarbamides and 1.5 g（7.81mmol）Lemon
Lemon acid is added in 50 mL deionized waters, stirring and dissolving to uniform solution；
（2）By step（1）Acquired solution is poured into 100 mL polytetrafluoroethylene (PTFE) pyroreaction kettles, and box hat sealing is placed in air blast baking
In case, 160 DEG C are heated to, reacts 20 h, cooled to room temperature, filtering is taken up in order of priority intersection with ethyl alcohol and deionized water and is washed
It washs filtrate 4 times, then is placed in 80 DEG C of convection ovens, dry 12 h obtain black powder；
（3）By step（2）Gained black powder is in high pure nitrogen atmosphere, at 500 DEG C, roasts 4h, naturally cools to room
Temperature obtains pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material.
After testing, the zinc sulphide in pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material obtained by the embodiment of the present invention and
Ferrous sulfide is pure phase, without other impurity.
After testing, the second particle of pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material obtained by the embodiment of the present invention is big
Small is 6~8 μm, and the duct containing 0.5~1.5 μm of diameter.
The assembling of battery：Weigh pore sphere zinc sulphide/ferrous sulfide/Carbon anode material obtained by the 0.40g embodiment of the present invention
Material, addition 0.05g acetylene blacks make conductive agent and 0.05g N-Methyl pyrrolidones make binder, after mixing, are applied to copper foil
On negative plate is made, in vacuum glove box with metal lithium sheet be anode, using lithium electric separator as diaphragm, 1mol/L LiPF6/EC:
DMC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
It will be appreciated from fig. 6 that being 3~0.01V in charging/discharging voltage, current density is under 50mA/g, and institute's assembled battery is for the first time
Specific discharge capacity is 969.3 mAh/g, and initial charge specific capacity is 772.7 mAh/g, and head effects are 79.7%.
After testing, it is 3~0.01V in charging/discharging voltage, current density is under 1 A/g, and institute's assembled battery is recycled to 1000
After circle, specific discharge capacity remains at 722.3 mAh/g, and coulombic efficiency is 97.7 %, illustrates material energy in charge and discharge process
The stabilization of enough holding structures, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
Claims (6)
1. a kind of pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material, which is characterized in that be made of following methods：
（1）Source of iron, zinc source, sulphur source and ternary organic carboxyl acid are added to the water, stirring and dissolving to uniform solution；
（2）By step（1）Acquired solution seals, and carries out heating reaction, cooling, filters, and washs, dry, obtains black powder；
（3）By step（2）Gained black powder in an inert atmosphere, roasts, cooling, obtain pore sphere zinc sulphide/ferrous sulfide/
Carbon negative pole material.
2. pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material according to claim 1, it is characterised in that：Step（1）
In, the molar ratio of ferro element and Zn-ef ficiency in zinc source is 1 in the source of iron:1~3；The sulphur source is rubbed with ferro element and Zn-ef ficiency
The molar ratio of the sum of your number is 1~5:1；The molar concentration of the sum of the ferro element and Zn-ef ficiency molal quantity in uniform solution is
0.08~1.0 mol/L；Molar concentration of the ternary organic carboxyl acid in uniform solution is 0.08~1.0 mol/L.
3. pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material according to claim 1 or claim 2, it is characterised in that：Step
（1）In, the source of iron is organic source of iron；Organic source of iron be ferric acetyl acetonade, ironic citrate or ferrocene in one kind or
It is several；The zinc source is inorganic zinc source；The inorganic zinc source is zinc sulfate, zinc nitrate or zinc chloride and their hydrate
One or more of；The sulphur source is organic sulphur source；Organic sulphur source is in thioacetamide, thiocarbamide or L-cysteine
One or more；The ternary organic carboxyl acid is citric acid and/or Trimesic acid.
4. according to one of claims 1 to 3 pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material, it is characterised in that：
Step（2）In, the temperature of the heating reaction is 120~250 DEG C, and the time is 6~24 h.
5. according to one of Claims 1 to 4 pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material, it is characterised in that：
Step（2）In, the mode of the washing is to be taken up in order of priority cross washing filtrate >=2 time with ethyl alcohol and water；The temperature of the drying
Degree is 60~100 DEG C, and the time is 10~40 h.
6. according to one of Claims 1 to 5 pore sphere zinc sulphide/ferrous sulfide/carbon negative pole material, it is characterised in that：
Step（3）In, the temperature of the roasting is 400~600 DEG C, and the time is 2~6h；The inert atmosphere is argon gas or nitrogen gas
Atmosphere.
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| CN112993221A (en) * | 2021-02-04 | 2021-06-18 | 多助科技(武汉)有限公司 | Preparation method and application of titanium dioxide/carbon/ferrous disulfide composite material |
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| CN112993221A (en) * | 2021-02-04 | 2021-06-18 | 多助科技(武汉)有限公司 | Preparation method and application of titanium dioxide/carbon/ferrous disulfide composite material |
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